Cyclic acetylenic hydrocarbon preparation



United States Patent 3,296,321 CYCLIC ACETYLENIC HYDROCARBON PREPARATIONBobby F. Adams, Painesville, and John H. Wotiz, Mentor,

Ohio, assignors to Diamond Alkali Company, Cleveland, Ohio, acorporation of Delaware No Drawing. Original applieationAug. 6, 1959,Ser. No.

831,930, now Patent No. 3,207,804, dated Sept. 21,

1965. Divided and this application Dec. 11, 1964, Ser.

15 Claims. (Cl. 260-666) This is a division of application Serial No.831,930, filed August 6, 1959, now US. Patent No. 3,207,804, issuedSeptember 21, 1965, which in turn is a continuation-in-part ofapplication Serial No. 769,583, filed October 27, 1958, now US. Patent3,052,734, issued September 4, 1962.

This invention relates to novel polyynes comprising linear alpha, omega,polyacetylenic hydrocarbons and cyclic polyacetylenic hydrocarbonsprepared by'chemically reacting an organic dihalide with a compound conhtaining the linkage C=C, and to novel methods of preparing and usingpolyynes.

The present invention comprises the process illustrated by the followingequation and certain novel products thereof:

Patented Jan. 3, 1967 "ice as well as corresponding ortho and metaradicals, oxygen, sulfur, mercury, boron, boron-containing radicals suchas y o m a B halogen to 4-nlkyl heterocyclic radicals such as arylsubstituted alkylene radicals, e. g.,

u cEo-E(GH2),(R molsn),o;.o3M X(oH2)e(R )i( Hz)= d (I) (II) I I(ormqHozo-aom). Lit -CEO'-E'(GH2)n )b (C 2)efCEO-}T( H2)e )F'"( 2)g 1-,l-,(R)s y, l l d y Han-C501 (4311,

(III) (IV) wherein M M M and M are the same or difierent substitutedalkylene radicals, e.g'., and are selected from the group consisting ofcopper, oalkl H alkali metals, i.e.. sodium, potassium, rubidium,lithium and cesium; alkaline earth metals, i.e., calcium, strontium andbarium; and hydrogen; with the proviso that only one of M and M can behydrogen; a is a number from 0 to 20, inclusive; b is a number from O to2, inclusive; 0 is a number from 0 to 20, inclusive; with the provisothat when b is 0 or 1, either a or c is equal to or greater than 3 orthe sum of a and c is equal to or greater than 3; d is a number from 0to 20, inclusive; e is a number from 0 to 20, inclusive; 1 is a numberfrom 0 to 2, inclusive; with the proviso that when f is 0, the sum of eand g is equal to or greater than 3; g is a number from 0 to 20,inclusive; y is a number from 1 to 10,000; X is chlorine, bromine,iodine or tosyl radical R and R are the same or different radicalsselected from the group consisting of alkylcne, e.g., radicals havingthe structure -C H (and corresponding branched chain radicals), whereinm is a number from 1 to arylene,

alkyl 1 to 4 wherein M isselectedfromthe groupconsistingof calcium,barium, z inc, tin, lead,

| BP-CHzCHzCHPSF-C HzCHaGHzCHn-Br Cl (CH Cl Novel linear compounds ofthis inveniton are hydrogenended compounds having the followingstructure:

wherein M M, a, b, c, d, e, f, g, y, R and R are as definedhereinbefore. T

A preferred linear polyyne of this invention'has the structure:

wherein Z is an alkalene radical, h is a number from 3 to 10, inclusive,and i is a number from 2 to 10, inclusive.

The term alkylene radical as employed in the specification and claims,unless otherwise defined,- is intended to refer broadly to organichydrocarbon radicals having the general formula C H m being a numberfrom 1 to about 50, inclusive, e.g., 1 to 20, which radicals may beeither straight chain or branched chain, e.g., those having 2 to carbonatoms. Specific examples of allHa Hr-CH:

112-011: More particularly, preferred lower molecular weighthydrogen-ended alpha, omega polyacetylenic hydrocarbons, e.g., alpha,omega triacetylenic and alpha, omega kylene radicals are thosecontaining 5 carbon atoms, e.g.:

tetraacetylenic hydrocarbons of this invention may be represented by thestructure:

wherein n is a number equal to or greater than 1, e.g., a number from 1to about 15, inclusive, R and R are alkylene radicals containing from 2to about 15 carbon atoms, e.g., polymethylene and branched chainpolymethylene radicals, such as ethylene, trimethylene, tetramethylene,pentamethylene, heptamethylene, propylene, butylene, and the like.

Novel alpha, omega triacetylenic hydrocarbons of this invention may berepresented by the structure:

(VI) HCECR7-CECR8CECH wherein R and R are alkylene radicals containing 2to about 50 carbon atoms, inclusive. Specific illustrative triacetylenichydrocarbons of this invention are:

1,9, l7-octadecatriyne 1,8,15-hexadecatriyne 1,7,13-tetradecatriyne1,6,11-dodecatriyne Further illustrative linear compounds of thisinvention are alpha, omega tetraacetylenic hydrocarbons which may berepresented by the structure:

wherein R R and R are alkylene radicals containing from 2 to about 50carbon atoms, inclusive. Specific i1- lustrative tetraacetylenichydrocarbons within structure VII are:

1,7,13,19-eicosatetrayne 1,8,15,22-tricosatetrayne 1,9, 17,25-hexacosatetrayne 1,10,19,28-nonacosatetrayne Novel cyclic compounds ofthis invention have the following structure:

wherein n is a number equal to or greater than 1, e.g., a number from 1to about 15, R and R are alkylene radicals containing at least 5 carbonatoms, and x is a number from 1 to 20, inclusive.

Still more specifically, preferred novel cyclic acetylenic hydrocarbonsWithin the scope of this invention may be represented by the structure:

wherein R and R are alkylene radicals having at least 5 carbon atoms,e.g., 5 to 50 carbonatoms. Specific illustrative cyclic acetylenichydrocarbons within the scope of the structure IX are:

1,7-cyclotridecadiyne 1,8-cyclotetradecadiyne 1,9-cyclopentadecadiyne 51,10-cyclohexadecadiyne 1,7, 13 -cycloctadecatriynel,8,l-cycloheneicosatriyne 1,9,l7-cyclotetracosatriyne 6 METHOD A L E(XI) X(CH2)nX Na-CEC-Na (XII) Thus, such compounds can be prepared viathe reaction: 5 1 C50 -II'C C- (CI 2)nCEC H (GHQ 3 ((111),. X CH 1Xrr-ozo-rr L Jr l i) 1 1,0 (x is even or odd) l 0:0 (XIII) (XIV) l METHODB HOEC-E(CH2) CEC-:} H ru)p (CH3) X orr, ,.X Na-GEC(CHr)nC C- i I EIland/or {fig} n L o 0% XIII x v when x=odd number (even number of triplebonds) wherein M is as previously defined and preferably an N g: galkali metal, e.g., Na, X is chlorine, bromine or iodine, l qggmx a a 2m is a number from 3 to 40, m is a number from 3 to 40, 2ONfiCECWHQmCECH n is a number from 1 to 10,000, p is a number from 5 I" It to 40, and q is a number from 5 to when a large value =Q(CH:)NOCIHV+of n is desired, no MCEC-H is employed. 0:0

Polyynes of this invention can also be prepared using a polyacetylide asa reactant (I), e.g., mm) 01mm X(CH2),X M-ozo orn ,o0- \CE/g Compound XIis employedas a reactant when it is desired to minimize the formation ofhigh molecular l weight products; when it is omitted, a polymericproduct [J XIII and XIV are formed. Appropriate ll'gixtures of XI '1 andXII can be prepared by metering a nown v0 ume H (0119 of acetylene in toa suspension of NaNH (from weighed L l amount of Na) in liquid NI-I e.g.

q 3HCEC-H+5NaNH NaC: -CNa+ NaCECI-I wherein M is a metal, cg Na r is anumber f m 1 to An equivalent excess of I, XI and XII over the reactants40 s is a number f 1 to 40 and n is an odd number II and X is desirableto minimize the amountof halogengreater than one; p and q being asalready defined. 40 terminated p yy a m I As indicated previouslyhereinbefore, Compounds III (XV) HCEC{(CH -CEc} -(CH halOgI1 and V ofthis invention can he PFOdUCed y reacting a The thus-obtained alkalimetal ended products are concompouhd Producing the linkage and a dihaloverted to hydrogen-terminated products during the typical alkylehe; morebroadly Stated, such'compouhds can he work-up of the reaction,,e.g.,addition (as by washing) produced by reacting Compounds I and II. a ofwater causes hydrolysis.

The expression p und P C g the linkage Referring to Methods A and B, ahigh concentra- -CEC is intended to refer to compounds which i f N cb fC f Produce the linkage in the reaction Y vors the formation of cyclicproduct, whereas a high con- Although the preferred compounds of thistype are dicentrationof NaCEC-H (absence of alkali metal acetylides,such as disodium, dilithiurn and/ or dipotassium acetylides, theexpression is not to be so favor r r d t If N H t limited since it isintended to refer broadly to mono th S S 1 6;: 3 prism and polyacetylidecompounds providing the desired pro b 7 2 g d 0 mear CEC- linkage, e.g.,alkaline earth acetylides such r p yyne e orme owever Secon ary reac' ascalcium, barium, strontium, beryllium and magnesium Hons sue as aacetylides. For convenience in describing the invention, 2)H H\-particular reference will be made hereinafter to alkali 2)n -l- E metalacetylides as illustrative of such reactants and as may be responsiblefor the presence of linear polyynes constituting a presently preferredtype of reactant. in cases which do not contain any NaCEC Na.

The following two equations more specifically illus- Some representativeproducts of this invention are set trate the reactions involved: forthin the following table:

Polyyne Type 11 x M.P.G. B.P. C. Mm. Method A A B A A 1 A VIII l 3 71215 0.2 B z)A 2)r-O O(CHZ)4CEC(CHQ)-L 75 A cH (orn i 7 83 0.08 c

Furthermore, if one reacts X(CH ),,X with given ratio of mono todisodium acetylide (say 1:1), the yield of cyclic product increases withan increase in dilution. For example, the same quantity of reactants inone liter of solvent, e.g., NH will yield less cyclic product than thecorresponding reaction in liters of solvent. Higher dilution separatesthe molecules giving less chance for intermolecular interaction (linearproduct). If a molecule has a functional group capable of interaction,e.g., NaCEC(CH C.= C(CH X, then intramolecular reaction (formation ofcyclic product) is favored by higher dilution. However, if the tworeactive ends cannot get together (because of size or shape of themolecule), no cyclic product will be formed no matter what dilution isemployed. Thus, the amount of cyclic product will also depend on thevalue of n in X(CH ),,X. Specifically, we find that intramolecularreaction is the favored reaction when 11:5. The product1,8-cyclotetradecadiyne, is formed in relatively high yield even'over awide range of mono to disodium acetylide ratios. Conversely, a linearproduct is favored in concentrated solutions, absence (or lowconcentration) of chain stoppers (e.g. NaCECI-I) and with moleculesWhere reactive ends are not likely to self-condense.

The dialkali metal acetylide may be prepared by any convenient method;for example, the following empirical equations illustrate several othermethods for the preparation of this compound, any one of thesepreparations being satisfactory.

2Na+HC ECH NaCECNa 2NaNH +HCECH NaCECNa NaCECH+NaNH NaCECNa A discussionof the preparation of disodium acetylide, sodium amide, and of the abovereactions may be found in Inorganic Synthesis, vol. 2, Editor-in-ChiefW. Conrad Fernelius, the McGraW-Hill Book Company, Inc., New York 1946),pages 75 and following.

The polyynes of this invention may be prepared by chemically reactingseparately prepared dialkali metal acetylide and an alkylene dihalide orthey may be prepared in situ with the initial preparation of thedisodium acetylide, i.e., sodium and acetylene may be reacted in thepresence of ammonia followed by the addition of the alkylene dihalide,preferably in the same reaction zone.

A desired ratio mono to disodium acetylide can be established byadjusting the amount of acetylene that is introduced into a reactionvessel containing a given amount of NaNH e.g.,

3NaNH-g 2HCECH NaCECH NaCECNa 4NaNHz BHCECH 2NaO CH NaCEONa 5N1NH23HCECH NaCEOH QNaOECNa Since NaNH is prepared in quantitative yield bythe reaction of sodium with ammonia, the weight of used sodiumdetermines the amount of NaNH present. Acetylene is measured with wettest gas meter, 1 mole(STP)= 22.4 liters.

As stated, the disodium acetylide may be prepared in a reaction zoneseparate from the reaction zone in which the disodium acetylide isreacted with the alkylene dihalide. Exemplary of this is the preparationof compounds wherein 2 moles of the disodium acetylide previouslyprepared in a separate reaction zone are reacted with l to 3 moles ofthe alkylene dihalide. These reactants are combined in essentiallystoichiometric ratios; however, considerable departure from these ratiosmay be tolerated, such as up to about %15% departure from these ratios,without serious detriment to either quality of product or yield; anequivalant excess of the disodium acetylide being preferred when ahydrogen-ended product is desired.

This reaction is typically and advantageously carried out in a polarsolvent such as anhydrous liquid ammonia; other solvents which may beemployed are butylamine, ethylenediamine, triethylamine,tetrahydrofuran, dimethylether of diethylene glycol, dimethylether,dimethylformamide, dimethylacetamide, methyl pyrolidone, ethyl acetal,and dioxane or mixtures of the foregoing, e.g., a mixture ofdimethylformamide and tetrahydrofuran. Such solvents also may be dilutedwith neutral solvents such as ethyl ether or other aliphatic or aromaticsolvents.

The reaction temperature generally is dictated by the solvent employed,e.g., reaction is typically carried out at the reflux temperature of thesolvent or solvent mixture; a temperature of 30 to -35 C is typical whenemploying liquid ammonia. to 200 C. may be used. If necessary,superatmospheric pressures of up to about 40 atmospheres are generallysatisfactory; if desired, higher pressures also can be used. Thereaction occurs in a period of about 1 to 48 hours, typically 1 to 24hours, the exact reaction time depending on a number of factors, e.g.,solvent, reactivity of halide (I Br Cl) and especially temperature.

The desired polyacetylenic hydrocarbons can be isolated upon reactioncompletion by adding water or other proton donor solvents, e.g.,alcohols such as methanol, ethanol,

propanol, butanol and isopropanol and acids such as Ca+ 2N3. QNH;2N3NII: H3 zNaNr-r, HCECH NaGECNa 2NH'.

NaOEONa XRX Compound III and IV wherein XRX is compound II, definedpreviously. Al though liquid ammonia is the preferred solvent for thesereactants, other organic solvents, such as amines, e.g.,

butylamine, ethylenediamine, triethylamine and diethyl:

amine, tetrahydrofuran, and ethers such as dimethylether, diethylether,dimethylether of diethylene glycol and dimethylformamide dioxane,mixtures of the foregoing, ,or any of the polar solvents previouslyreferred to herein, e.g., a mixture of dimethylformamide andtetrahydrofuran may be employed' The reactants are mixed in the orderindicated in the above equations at a temperature dictated 'by thesolvent employed, but typically at a temperature of about 100 C. to 200C., e.g., 35 C. to +25" C. Normally, an equivalent excess of theacetylide reactant is employed; also, an excess of NH when employed assolvent may be desirable. The reaction is typically carried tocompletion over a period of about 3 to 36 hours. Isolation of theproduct may be carried out by means common in the art, such asrecrystallization from an organic solvent, e.g., petroleum ether,methanol, diethyl ether, benzene, ethanol, propanol and the like; thedesired product may also be isolated through distillation typically atreduced pressure or through either liquid or vapor phase chromatography,

Specific illustrative preparations involving the reaction of disodiumacetylide and an alkylene dihalide are the preparation of compounds ofstructures VI and VII above. Although the preferred preparation of thesecompounds VI and VII comprises chemically reacting disodium acetylideand an alkylene dihalide, the disodium acetylide 'being prepared in thesame reaction zone, these reactants may be prepared and combined inseparate reaction zones, i.e., the disodium acetylide may be prepared ina reaction zone separate from that employed in the reaction of di-However, temperatures of 9 sodium acetylide, and the alkylene dihalide.Typical reaction conditions in the preparation of alpha, omega triandtetraacetylenic hydrocarbons are as follows: 2000 to 5000 parts byweight of liquid ammonia is mixed with l to parts -by weight of acatalyst, e.g., ferric nitrate, iron oxide, or sodium peroxide; followedby the addition of 50 to 100 parts by weight of sodium metal to formsodium amide; 50 to 100 parts by weight of acetylene gas is then addedto this mixture. 2 to 4 moles of an alkylene dihalide is added at a ratesufficient to maintain a gentle refluxing of the ammonia. Upon reactioncompletion, 100 to 2000 parts by weight of water are added slowly to thereactant mixture with agitation.

The desired product is isolated by recrystallization from an organicsolvent, such as petroleum ether, methanol, ethanol, propanol, diethylether or benzene, the resultant product being further distilled atreduced pressure yielding the desired triand tetraacetylenicallyunsaturated compounds.

Illustrative of the foregoing and other specific compounds of thisinvention arethe following compounds having the indicated structures:

cEccH cEc H 1,8,15,22-tricosatetrayne 1,7,13,19,25-hexacosapentayne LCEC 1,8-cyclotetradecadiyne i-C EC-1| 61195 (CH2):

-OEG- 1,8-cyclopentadecadiyne ||CEO (CH2) a (01305 101,9-cyclohexadecadiyne CEC Compounds within the scope of structures VIIIand IX may be prepared by chemically reacting a dialkali metalacetyli-de and an alkylene dihalide under essentially the same reactionconditions employed for the preparation of a. linear alpha, omegapolyacetylenic hydrocarbon; that is, the cyclic hydrocarbon may be andis normally prepared as a by-product in the preparation of the linearhydrocarbons. The formation of this cyclic hydrocarbon is enhanced byincreased dilution of the initial starting materials, typicalproportions being about 4000 to 8000 parts by weight of solvent, 70 toparts by weight disodium acetylide, and 1 to 2 moles of alkylenedihalide.

The specifically preferred preparation at present is the reaction ofdisodium acetylide, prepared either in the same reaction zone or in adiiferent reaction zone, with a polymethylene dibromide, this reactiontaking place in the presence of a solvent, typically liquid ammonia,under the same reaction conditions given previously.

Fractional vacuum distillation is used if the boiling points are belowthe decomposition temperatures. Pot temperatures up to 350 C. are used.Fractional crystallization from conventional solvents, e. g., petroleumether, can be used in cases where the products have close boilingpoints, e.g.,

CEO (CH2)5 (CHM HCEC (CH2)5OEO(CHQ)5GECH CEO Solid Liquid linear Hgderivatives no reaction The linear polyynes may be regenerated onacidification with dilute HCl.

this invention exhibit activity as insecticides, fungicides,

herbicides and nematocides.

While compounds of this invention may be employed in a variety ofapplications, biologically active or otherwise, when employed asbiologically active materi-als it will be understood, of course, thatsuch compounds may be utilized in diverse formulations both liquid andsolid including finely-divided powders and granular materials as well asliquids such as solution, concentrates, emulsifia ble concentrates,slurries and the like, depending upon the application intended and theformulation media desired.

These compounds may be used alone or in combination with other knownbiologically active materials such as other acetylenically unsaturatedcompounds, organic phosphate pesticides, chlorinated hydrocarboninsecticides, foliage and soil fungicides, and the like.

Thus, it 'will be appreciated that compounds of this invention may beemployed to form biologically active substances containing suchcompounds as essential active ingredients which compositions may alsoinclude finelydivided dry or liquid carriers, extenders, fillers,conditioners, including various clays, suchastalc, spent catalyst,alumina silica materials, liquids, solvents, diluents or the like,including water and various organic liquids such as benzene, toluene,chlorinated benzene, acetone, cyclohexanone, chlorinated xylene, carbontetrachloride, ethylene dichloride, tetrachloroethylene, carbondisulfide, and alcohols at various temperatures'thereof.

When liquid formulations are employed or dry materials prepared whichare to be used in liquid form, it isvdesirable in certain instancesadditionally to employ a wetting, emulsifying or dispersing agent tofacilitate use of the formulation, e.g., Triton X-155 (alkyl arylpolyether alcohol, US. Patent 2,504,064). Other suitable surface activeagents may be found in an article by John W. McCutcheon in Soap andChemical Specialties, vol. 4, Nos. 7-10 (1955).

The term carrier as employed in the specification and claims is intendedto refer broadly to materials constituting a major proportion of abiologically active or other formulation and hence, includesfinely-divided materials both liquids and solids, as aforementionedconveniently used in such applications.

Moreover, the present invention relates to pesticidal compositionscontaining the acetylenic hydrocarbons of this invention, e.g.,1,7,l3,19,25-hexacosapentayne as a contact poison for bean beetles, andto methods of killing pests employing these compositions.

Still further, the compounds of this invention are useful in theinhibition of decomposition of a halogenated aromatic hydrocanbon. Inthis application it has been found that decomposition of a halogenatedhydrocarbon, e.g., a chlorinated xylene, may be prevented by theaddition thereto of a stabilizing amount of a compound according to thestructure:

wherein n is a number equal to or greater than 1, e.g., a number from 1to about 15, inclusive, R and R are alkylene radicals having greaterthan 4 carbon atoms, e.g., 1,8,15-hexadecatriyne. It has also been foundthat compounds within the scope of structure VIII are particularlyuseful in the stabilization of benzyl chloride,,the preferred compoundin this application being 1,8-cyclotetradecadiyne.

It is known that a chlorinated xylene in a pure condition may be storedor shipped with little or no decomposition induced by exposure to air,light, heat and/or moisture. However, in many instances obtaining suchhigh purity chlorinated xylene in commercial production is not feasible.xylenes normally encountered in commerce are subject to some degree ofdecomposition when in contact with substances such as specks of rust oraluminum, dirt, air, light, heat, moisture and the like. Hence, meansfor preventing and/or inhibiting this decomposition of chlorinatedxylenes and/or other chlorinated aromatic hydrocarbons generallyassociated therewith are highly desirable.

Previously various stabilizers for aliphatic chlorinated hydrocarbonshave been employed. Some of those compounds which have demonstrated adegree of effectiveness are acetylenic alcohols, acetylenic ethers,straight chain acetylenic esters, monoacetylenic hydrocarbons andmonoacetylenic monoolefiuic hydrocarbons. these prior stabilizersenjoyed a certain amount of success, surprisingly, such materials arenot satisfactory for the stabilization of chlorinated xylenes andspecifically alpha-chloro-p-xylenes for various reasons. Acetylenicalcohols are highly effective for the stabilization of such chlorinated.aliphatic hydrocarbons as perchlorethylene but are ineffective for thestabilization of chlorinated xylenes such as alpha-chloro-p-xylenes inthat significant decomposition occurs even though thealpha-chloro-pxylene contains relatively large quantities of thesecompounds. Monoacetylenic monoolefinic hydrocarbons and straight chainacetylenic esters are unsatisfactory for the same reason.

In view of the fact that the above acetylenically unsaturated generalstabilzers employed are unsatisfactory,

it would lead to the conclusion that the compositions employed in thestabilization of chlorinated xylenes and the method of statibilizingsuch compounds are highly selective, and, therefore, those stabilizersemployed previously in the stabilization of chlorinated aliphatichydrocarbons, such as carbon tetrachloride, perchlorethylene, tetrachlorethylene and the like, are not adaptable to the stabili-Unstabilized quantities of halogenated aromatic hydrocarbons asproduced, including such compounds as alphachloro-p-xylene and benzylchloride, may be either in a relatively pure or impure condition. Forthe most part the purity of such halogenated aromatic hydrocarbondepends uponits age, i.e., the length of time it has stood unstabilizedafter production without particular eiforts being made to prevent thedecomposition. Accordingly, a relatively impure halo aromatichydrocarbon is found to be of limited utility for many industrial needsalthough further decomposition may -be inhi bted by using ,thestabilizers for the present invention. On the other hand, someunstabilized halo'aromatic hydrocarbons are employed while relativelyfresh and are correspondingly pure and usable. Such materials requireonly stabilization against further decomposition in order to besatisfactory for a number of uses.

Where the initial purity is not tolerable the chlorinated aromatichydrocarbon may. require pretreatment of .a nature such that the majorproportion or substantially all of the impurities are removed prior tothe addition of stabilizers so as to provide a material having a goodinitial level of acceptability for industrial needs. As noted above,some chlorinated aromatic hydrocanbons may not require such pretreatmentalthough those skilled in the art will understand that a chlorinatedxylene containing undesirable impurities may advantageously be treatedfor the removal or reduction of any impurities prior to stabilization.Such purifications may be effected through means common in the art, suchas distillation.

It has been found that the chlorinated,

Although i In general, the present invention is directed to acomposItion comprising essentially a chlorinated aromatic hydrocarbon,e.g. a normally liquid chlorinated xylene, such as alpha-chloro-p-xyleneand a stabilizing amount of at least one polyacetylenic hydrocarbon,i.e., triacetylenic hydrocarbon and tetraacetylenic hydrocarbon,preferably 1,8,15-hexadecatriyne.

Further, the present invention is directed to a composition comprisingessentially benzyl chloride and a stabilizing amount of at least onecyclic acetylenic hydrocarbon, e.g., 1,8-cyclotetradecadiyne.

Further, the invention is directed to such a composition including anadditional ingredient efiective to exert a stabilizing action againt theinfluence of light and other sources of decomposition. This is intendedto include other stabilizers which may be combined with the stabilizersof the present invention which cause a synergistic effect concerning thestabilization of halogenated aromatic hydrocarbons. Typical stabilizercombinations of 1,8,15-

hexadecatriyne and bis-(Z-propynl)-2,3,5,6-tetrachloroterephthalate,1,8,15-hexadecatriyne and sorbitol, and 1,8- cyclotetradecadiyne andethylene glycol. It will be understood that the invention is not limitedto a particular light, heat, or other stabilizers, and that, in general,any well-known light or other stabilizer may be employed with thegeneral purpose stabilizers of this invention.

As stated, a new class of stabilizers noted above, namely, alpha, omega,triand tetraacetylenic hydrocarbons have been found particularlyeffective in stabilizing alpha-chloro-p-xylene contaminated with minoramounts of metallic ions, such as those produced by specks of rust oraluminum, both in a liquid or in a vapor phase. For the most part, thestabilizing effect has been found to be most pronounced and prolongedwhere pretreatment which removes the greater part of contaminatingmetallic ions has been resorted to prior to the addition of thestabilizing alpha, omega, trior tetraacetylenic hydrocarbon.

The method of stabilizing halogenated aromatic hydrocarbons, i.e.,chlorinated aromatic hydrocarbons, in accordance with this inventioncomprises essentially contacting a major proportion of the halogenatedaromatic hydrocarbons, i.e., the chlorinated xylenes or benzyl chloride,with a stabilizing amount of the alpha, omega polyacetylenic hydrocarbonor the polycycloacetylenic hydrocarbon, respectively. It is preferredthat the stabilizer be added after the initial preparation of thehalogenated hydrocarbon, i.e., after the chlorination step, and that thestabilizing amount of the respective stabilizers be combined, as notedabove e.g., in an amount of about 0.0001% to by weight of thehalogenated aromatic hydrocarbon, preferably, however, from about 0.1%to 1% by weight of the chlorinated aromatic hydrocarbon. Under moreadverse conditions, such as higher temperatures and/or excessivecontamination, it may be necessary to add several percent of thestabilizer. Large quantities of the stabilizer are seldom necessary ordesirable and in most cases amounts of stabilizer less than 5% by weightof the halogenated aromatic hydrocarbon protect the halogenated compoundagainst the decomposition under the most severe conditions normallyencountered. The indicated intermediate preferred range is generallysufficiently effective for the purified halogenated aromatic hydrocarboncontaining not more than 0.2% by weight of the metallic impurities mostcommon in commercial production.

Other applications of compounds of this invention include polymers,solid rocket fuel binders, coatings, films, fibers, intermediates,polymerization catalysts, high energy fuels, rocket fuelstarters,'plasticizers, stabilizers, and the like.

Other applications and uses will be apparent to those skilled in the artin view of the following specific examples. These examples are offeredin order that those skilled in the art may more completely understandthe present invention and the preferred methods by which the same may becarried into effect.

Example 1.-Preparation 0f 1,8-cyclotetradecadiyne 2.5 liters of liquidammonia is placed in a flask, followed by the addition of 1.35 g. offerric nitrate hydrate (0.3 g. for each g. atom of sodium employed). 2.0g. of sodium metal is then added and activated by bubbling dry air intothe mixture. 103.5 g. (4.4 mol) of sodium metal is added in smallportions and 54.3 liters (2.2 mol) of acetylene gas at 28 C. and 747 mm.mercury pressure is bubbled into the suspension of the sodium amide and500 g. (2.2 mol) of pentarnethylene dibromide is added at a fastdropwise rate sufiicient to retain gentle refluxing ammonia. Uponcompletion of addition of the dibromide, agitation of the mixture isincreased to wash down the splattered material on the sides of thereaction flask. The reaction is then stopped and the openings of thereaction vessel covered with polyvinyl chloride film, the reactionmixture being allowed to stand overnight. The reaction mixture is thenagitated while water is added slowly with caution. The pressure isvented by loosening the plastic sheets covering the reaction vesselopening. Upon addition of about 400 ml. of water, the reaction vesselwalls are washed by increasing the agitation. The resultant gummy solidis found to be soluble in organic solvents, i.e., pentane and ether.Isolation of the desired acetylenic cyclic hydrocarbon is accomplishedby recrystallization from ether, yielding not only the cyclichydrocarbon but also the respective triand tetraacetylenicallyunsaturated compounds as by-products. The crude product is furthervacuum distilled and recrystallized from ether, yielding the desiredproduct melting at 99 to 100 C. This C H having a molecular weight of188.3, is indicated by the following elemental analytical data:

Element Actual Percent By Weight Calculated Percent By Weight Infraredspectra indicate the presence of internal acetylenic linkage and theabsence of terminal acetylenic linkage; in addition, the compound isinsoluble in water and soluble in acetone, cyclohexanone and xylene.

Example 2 The procedure given in Example 1 is carried out separating the1,8,15hexadecatriyne distilling at to C. at .7 to 1.0 mm. mercurypressure. This triacetylenic hydrocarbon has a refractive index at 25 C.of n 1.4774, this O l-I being indicated by the following elementalanalytical data:

Element Actua] Percent By Weight Calculated Percent By Weight Infraredspectra also indicates the desired product.

Example 3.-Preparation of 1,7,I3-telradecatriyne and and1,7,]3,19-eic0satelrayne eicosatetrayne-S 15 evolved the stirrer isspeeded up to wash the flask walls free of spattered sodium. Acetyleneis then added to the mixture until the milky suspension begins to clear,typically about /2 to 2 hours. 648 g. (3.0 mol) of tetramethylenedibromide is then added at a rate to retain a gentle reflux of liquidammonia. Upon reaction completion, the ammonia is allowed to evaporate.About 200 to 300 mls. of water is then added with caution and the twolayers formed, i.e., the organic layer and aqueous layer, are extractedseveral times with 100 ml. portions of ether.

The combined ether extracts are washed with dilute -hy-- drogen chlorideand dilute sodium carbonate aqueous solutions and dried over calciumsulfate. Ether is then removed through distillation. The resultantproduct is distilled with 1,7,l3-tetradecatriyne, C H boiling at 111 to112 C. at 1.0 mm. mercury pressure and an additional product,1,7,13,19-eicosat6trayhe, cgoHge, boiling at 165 to 170 C. at 0.3 mm.mercury pressure. The above triyne is indicated by the followinganalytical data:

Element Actual Percent By Calculated Percent Weight By Weight 89.2 90. 2H 9. 6 0. 8 Molecular Weight 188 186 The above tetrayne .is alsoindicated by the following elemental analytical data:

Element Actual Percent By Calculated Percent Weight By Weight C S9. 390. 2 H 9. 8 9. 8 Molecular Weight 276 266 Other higher polyynes arealso formed as by-products of the above reaction. The desired productsare also indicated by infrared spectra.

Example 4 To further demonstrate insecticidal activity of 1,7,13,-19-eicosatetrayne, fourth instar larvae of the Mexican bean beetle,Epilachna varivestis, less than one day old within the instar, areemployed. Paired seed leaves, excised from Tender-green bean plants, aredipped in a formulation of the test chemical (2000 p.p.m. 1,7,13,19-

acetone0.0l% Triton Xl55- balance Water) until they are thoroughlywetted. The chemical deposit on the leaf is then dried and the pairedleaves are separated. Each is placed in a 9 cm. Petri dish with a filterpaper liner, and ten randomly selected larvae are introduced before thedish is closed. After three days exposure, 100% mortality is observed.

Example 6 In order to evaluate insecticidal activity of the compounds ofthis invention, male German cockroaches, Blattella germanica, 8 to 9weeks old, are anaesthetized with carbon dioxide to facilitate handlingand then dipped in a test formulation (2000 ppm. test chemical% 16acetone0.0l% Triton Xl55balance water) for 10 seconds, removed and freedof excess liquid, and caged. Two lots of 10 insects each are exposed tothis formulation and mortality observations are recorded after threedays. Using this procedure, the following mortality ratings areobserved:

TABLE I Percent roach mor- Example 7 Insecticidal utility of1,7,l3,l9-eicosatetrayne, i.e., one of the products of Example 3, isshown in the following test. The bean aphid, Aphis fabae, is cultured onnasturtium plants. No attempt is made to select insects of a given agein this test. Test pots are prepared by reducing the number ofnasturtium plants in 2 /2 inch culture pots until those remaining areinfested with approximately 100 aphids. The infested test plants aretreated with a formulation of the test chemical (2000 p.p.m. 1,7,13,19eicosatetrayne-5% acetone0.01% Triton X155balance water) Based on countsmade 24 hours after exposure greater than mortality is observed.

Example ,8

In order to evaluate systemic fungicidal activity, tomato plants,variety Bonny Best, growing in 4-inch pots are.

treated by pouring a test formulation (2000 p.p.m. product of Example15% acet0ne0.0l% Triton Xl55' balance water) on the soil in the pots ata rate equivalent to 128 lbs/acre (102 ing/pot). The tomato plants are 3to 4 inches tall and the trifoliant leaves are just starting to unfoldat time of treatment. The tomato plants are exposed to the early blightfungus so that at the time of treatment, infection has occurred. After10 to 14 days observation indicates greater than 45% disease control.

Example 9 Spore germination tests on glass slides are conducted via thetest tube dilution method adapted from the procedure recommended by theAmerican Phytopathological Societys committee on standardization offungicidal tests. In this procedure, the product of Example 2 in aqueousformulations at concentrations of 1000, 100, .10 and 1.0 p.p.m. istested for its ability to inhibit germination of spores from 7 to 10 dayold cultures of Alternaria oleracea and Monilinia fructicola. Theseconcentrations refer to initial concentrations before diluting fourvolumes with one volume of spore stimulant. and spore suspension.

Germination records taken after 20 hours of incubation at 22 C. bycounting spores. Based on a rating system whereby thelistedconcentration afi'ords disease control,

the following compounds were rated according to their activity in thistest:

1 7 Example A tomato foliage disease test is conducted measuring theability of the product of Example 2 to protect tomato foliage againstinfection by the early blight fungus Alternaria solani. Tomato plants 5to 7 inches high of the variety Bonny Best are employed. The plants aresprayed with 100 ml. of test formulation at 2000 p.p.m. (2000 p.p.m.product of Example 25 acetone0.01% Triton X-155balance water) at 40 lbs.air pressure while being rotated on a turntable in a spray chamber.After the spray deposit is dry, the treated plants and comparableuntreated controls are sprayed with a spore suspension containingapproximately 20,000 conidia of A. solam' per ml. The plants are held ina 100% humid atmosphere for 24 hours at 70 F. to permit sporegermination and infection. After 2 to 4 days, lesion counts are made onthe three uppermost fully expanded leaves. Data based on the number oflesions obtained on the control plants shows better than 75% diseasecontrol.

Example 11 To evaluate bactericidal activity, the test chemical is mixedwith distilled water containing 5% acetone and 0.01% Triton X-l55, at aconcentration of 250 p.p.m. 5 ml. of the test formulation are put ineach of four test tubes. To each test tube is added one of theorganisms: Erwenia amylovora, Xanthomonas phaseoli, Staphylococcusaureus and Escherichia coli in the form of a bacterial suspension in asaline solution from potato-dextrose agar plates. The tubes are thenincubated for 4 hours at 30 C. Transfers are then made to sterile brothwith a standard 4 mm. loop and the thus-innoculated broth is incubatedfor 48 hours at 37 C. Using this procedure the products of Example 3afford the noted bacterial control:

xample 3) 1,8,l5-l'11exadecatriyne (Product of Exa 18 about 4 inch ofsoil and watered. After 24 hours, 80 ml. of an aqueous test formulation(320 mg. test chemical 5% acetone-0.0l% Triton Xl55--balance water)uniformly over the surface of the pan. This is equivalent to 64lbs/acre. The seed mixture contains representatives of three broadleafs:turnip, flax, and alfalfa, and three grasses: wheat, millet, and ryegrass. Two weeks after treatment records are taken on seedling stand ascompared to the controls. Using this procedure the following results areindicated:

TABLE V Broadleaf Grass Plants Plants 1,7,13,19-eic0satetrayne (Productof amp 2) 1,7,13-tetradecatriyne Example 14 To test herbicidal activityof the product of Example 1, tomato plants, variety Bonny Best, 5 to 7inches tall; corn, variety Cornell Ml (field corn), 4 to 6 inches tall;bean, variety Tendergreen, just as the trifoliate leaves are beginningto unfold; and oats, variety Clinton, 3 to 5 inches tall, are sprayedwith an aqueous test formulation (6400 p.p.m. test chemical5%acetone0.0l% Triton X-lbalance water). The plants are sprayed with100ml. at 40 lbs. air pressure While being rotated on a turntable in aspray hood. Records are taken 14 days after treatment and phytotoxicityis rated on TABLE III Compound Tested E. Amylovom X. phaseoli S. aureusE. coli 1, 7, 13-tetradecatriyne- 90 70 40 10 1, 7, 13, l eicosatetrayne40 0 40 0 Example 12 a scale from 0 for no injury to 11 for plant kill;Using Seeds of green foxtail and lambs quarters are treated in Petridishes with aqueous suspensions of the test chemical at 1000 and 100p.p.m. (1000 or 100 p.p.m. product of Example 35% acetone-0.01% TritonX-l55balance water). Lots of 25 seeds of each type. are scattered inseparate dishes containing filter paper discs moistened with 5 ml. ofthe test formulation at each concentration. After 7 to 10 days undercontrolled conditions, the test compound is given a rating whichcorresponds to the concentration that inhibits germination of half ofthe spores (ED 50) in the test or greater. Using this test, thefollowing results are observed:

TABLE IV Concentration inhibiting germination of half of the seedsCompound Tested Lamb's Quar- Green Foxtail,

ters, p.p.m. p.p.m.

1,7,13-tetradecatriyne 100-1, 000 100-1, 000 1,7,13,19-eicosatetrayne 1,000 1001, 000

Example 13 To evaluate the effect of the compounds of this inventionupon the germination of seeds in soil, a mixture of seed of six cropplants is broadcast in 8 x 8 x 2 inch metal cake pans filled to within/2 inch of the top with composted greenhouse soil. The seed is uniformlycovered with eter x 8 mm. deep),

this procedure the product of Example 1 receives ratings of 2, '3, 11and l for the tomato, bean, corn and oat plants, respectively, thusdemonstrating selective herbicidal activity.

Example 15 Example 16 In order to demonstrate the effectiveness of astabilizer of the present invention, a procedure is carried out by whichalpha-chloro-p-xylene is stabilized with 1,8,15-hexadecatriyne. In thistest 25 ml. of alpha-chloro-pxylene is placed in each of six 4 ounceclear glass containers. 1,8,15-hexadecatriyne is added to the first fivecontainers in concentrations of 0.0125 g., .025 g., .125 g., .250 g.,and .500 g., respectively. A metal contaminant comprising 50% ironpowder and 50% iron oxide is then added in concentrations of from 0.01g. to 0.5 g. per container. A series of six solutions is made up in thismanner, the last solution being employedas a standardized check. Each ofthese solutions is allowed to stand at room temperature for 9 days inthe presence of ordinary room light whereupon each of the solutions israted on a scale from for colorless to 10 denoting completedecomposition and high discoloring. Employing this procedure, thestandard check solutions were completely black receiving .a rating of 10at the end of the period employed, whereas the stabilized solutions werecolorless, receiving a rating of 0. Thus demonstrating that 1,8,15-hexadecatriyne is singularly elfective in the stabilization ofalpha-chloro-p-xylene for a period of greater than 9' days under theconditions employed.

Example 17 To further demonstrate the effectiveness of a combination ofstabilizers of the present invention, a procedure is carried out bywhich alpha-chloro-p-xylene is stabilized with 1,8,15-hexadecatriyne andethylene glycol. In this test 25 ml. of the alpha-chloro-p-xylene isplaced in each of four 4-ounce clear glass containers. A combination of0.0125 g. of 1,8,15-hexadecatriyne and 0.0125 g. of ethylene glycol isadded to the first container. To the second a combination of 0.0625 g.of the triyne and 0.0625 g. of ethylene glycol is added and acombination of 0.125 g. of the triyne and 0.125 g. of ethylene glycol isadded to the third, respectively. A metal contaminant comprising 50%iron powder and 50% iron oxide is then added on concentrations fromabout 0.01 g. to 0.5 g. per container. A series of four solutions ismade up in this manner, the latter solution being employed as thestandardized check. Each solution is allowed to stand at roomtemperature for 16 days in the presence of ordinary room light,whereupon each of these solutions is rated on a scale from 0 forcolorless to 10 denoting complete decomposition and high discoloring.Employing this procedure the standard check solutions were completelyblack at the end of the period employed whereas the stabilized solutionswere colorless, receiving a rating of 0. Thus demonstratingthat thecombination of 1,8,l-hexadecatriyne and ethylene glycol issynergistically effective, stabilizing alpha-chloro-p-xylene for aperiod of better than 15 days under the conditions employed.

Example 18 A further demonstration of the effectiveness of the ceptionthat a concentration of .0625 g. of the triyne in combination with .0625g. of the alpha, omega diacetylenic ester is employed. This testindicates that at this concentration, the combination of the alpha,omega polyacetylenic hydrocarbon and the alpha, omega diacetylenicesters are efiective as stabilizers for alpha-.

chloro-p-xylene for a period of at least three days.

Example 19 Stabilizing eifectiveness of the product of Example 1 isdemonstrated by stabilizing benzyl chloride employing essentially thesame test procedure given in Example 16. In this test the cycliccompound is completely ineffective in stabilizing alpha-chloro-p-xylene,but all the solutions.

of benzyl chloride are colorless after a period of greater than 15 days.

Example 20.Preparation and alkylation of sodium acetylides Sodium (7mol) is reacted with 4 liters of anhydrous ammonia at 33 in the presenceof iron containing.

catalyst prepared by the method set forth in Organic Reactions, vol. 5,pp. 48-49. Dry acetylene is then metered into the suspension of sodiumamide in ammonia until the desirable ratio of mono to disodium acetylideis reached, i.e., 1:1 or 2:1. The dihalide is added dropwise and thereaction mixture stirred under reflux for four hours. The DryIce-acetone condenser is removed, the opening covered with a cellophanefilm, and the ammonia is permitted to evaporate over a 16-hour period.Thev residue is diluted with water and, if the organic portion is notsulficiently liquid, it is dissolved in ether. The organic layer iswashed, in succession, with dilute hYdlO'.

chloric acid, sodium carbonate, water and dried over.

magnesium sulfate. The products are separated by fractionaldistillation. In reactions where n is 5, the disti1la-.

tion is temporarily interrupted after the diyne and triyne (II, x=1 and2) are collected. On cooling, the cyclic.

diyne III (x=1) crystallizes and is removed by filtration.

Fractional distillations at 0.1 mm. are continued until a pot temperaureof 350 is reached. The pot residue is I frequently only tan-colored andof vasoline-like consistency. Fractions of narrow boiling range areredistilled 1 or crystallized from appropriate mixtures of ether-.

The products are characterized by petroleum ether.

stabilizers of the present invention is carried out by sta- Q boilingand melting points, index of refraction and in: bilizingalpha-chloro-p-xylene with a combination of 1,8, frared spectra.

TABLE I o NaCEC-.Na X a BHCHmBr H-c =.c-[ om).c=c- .-H (v (on. (0111)..(37111 Mo]. w ht Polyyne Type n x Calcd. Found Calcd. Found elg Calcd.Found v 4 2 90. a 89.2 9. 7 9. 0 186 188 v 4 a 90. 2 s9. 3 9. s 9. s 266276 v 4 7 90.1 88.5 9. 9 10.2 586 597 v 4 s 90. 1 86. 9 9. 9 10.2 666666 v= 5 2 89. 5 88. a 10. 3 10. 3 214 203 s 2 2 as as 1 9 308 0. 10.242 237 H-OEO(CHZ)O(CH;)4CECHI 81.0 79.4 101 9.9 178 164 VIII 5 1 89.389.6 10.7 10.6 198 182 VIII9- 4 3 90. 0 s9. 5 10. 0 9.8 320 270 prime E0(CH h-O 79. 0 79. 1 10.5 10.6 304 279 V See footnote at end of table.

TABLE IContinued Characteristic LR. Bands 13.1.

p (intensity) M.P., Polyyne Type C.

C E 0. mm. HO CH Hg (Rocking) Terminal Internal V 111 1.0 3.02vs.-.4.70m 4.47VW 13.62w. V 167 0. 3 3.02vs--. 4.70m 4.47vw 13.55W. V 363.05W 13.55VW. V 55 3.05W 13.55vw. Va--- 113 0.8 3.07vs 13.80111. V- 1700.1 33 3.02s V- 131 0. 2 24 3.04vs 13.82111. HC C(CH2)40 '(CH2)4C C H130 30 3.05vs VIIL 100 13.645. me 215 0. 2 71 13.60w. (CH2)4C C(CH) O175 0.1 75

O-(CHz)4C C (CH2);

Norm: An equivalent excess of about 25% to 50% Na over Br is used.

Sodium amide is prepared from 69 g. (3.0 mol) of sodium and 3 liters ofanhydrous ammonia, at its boiling point (-32), and in the presence ofiron containing catalyst. A 2: 1 mixture of N2.CECH to NaCECNa is thenprepared by the introduction of 2.25 moles of acetylene (measured withthe aid of a wet test .gas meter). The addition of 382 g. (1.0 mol) ofI(CH O(CH I is over a period of 4 hours. The stirred mixture is keptnear 32 While ammonia is permitted to evaporate through acellophane-capped outlet. The residue is diluted with water and theorganic layer washed with dilute HCl, and dried. Repeated fractionaldistillation yields:

(a) HCEC(CH2)40(CH2)4CECH, 19.5 g., colorless liquid, B.P. 130 at 30mm., n 1.4577.

Analysis.Calcd. for C H O: C, 81.0; H, 10.1; M.Wt. 178. Found: C, 79.4;H, 9.9; M.Wt. 165. The infrared spectrum contains the characteristicabsorption bands of CECH near 3.05 and 4.74,:1.

5 g., R1. 180 at 0.08 mm., M.P. 74-5 (colorless crystals).

Analysis.Calcd. for C H O C, 79.0; H, 10.5.

Found: C, 79.1; H, 10.6. The infrared spectrum shows it to be free ofabsorption bands characteristic of a terminal triple bond. The-internaltriple bond was evident from the absorption band near 4.5 0 1.

The 5-hexynyl ether exhibits activity as a contact poison againstroaches, as a systemic rust fungicide and as a bactericide.

Example 22.Preparati0n of Sodium amide is prepared from 47 g. (2.05mol') of sodium in 3 liters of liquid ammonia at 32. A 1:1 mixture ofNHCECH and Na-C-=-CNa is prepared by metering into the suspension 1.37moles of acetylene. Alkylation is effected by the addition of 200 g.(0.82 mol) of Br(CH) Br. Stirring is maintained for 48 hours Whileammonia is permitted to evaporate through a cellophane-capped opening.The residue is diluted with water and the organic layer washed withdilute HCl and dried. Repeated distillation yields 27 g. of colorlessliquid, B.P. 1309 at 0.2 mm., 11 1.4772 to 1.4806,

I spectrum contains bands near 3.04 and 4.72 characteristic of terminaltriple bonds. 7

Example 23.Prepara1tion of H--CEc(CH )5CEC(C H CEC(CH 5CECH Sodium amideis prepared from 23 g. (1.0 mol) of sodium and 2 liters of liquidammonia at 32. To this suspension is added 211 g. (1.75 mol) ofHCEC(CHZ) CECH" The product is alkylated with 69 g. (0.3 mol) ofBY(CH2)5BI The suspension is stirred for 16 hours while ammonia ispermitted to evaporate through a. cellophane-capped opening. The residueis diluted with water and the organic layer washed with dilute HCl anddried. Distillation results in the recovery of 144 g. of the startingnonadiyne, and 26 g. of 1,8-cyclotetradecadiyne. Further distillationyields a fraction boiling from 170 at 0.1 -mm., which solidifies oncooling to room temperature. Crystallization of this fraction from ethergives 25 g. of the solid l,8,1S,22-tricosatetrayne, M.P. 32-3".

Analysis.-Calcd. for C H C, 89.6; H, 10.4; M.Wt. 308. Found: C, 89.1; H,10.6; M.Wt. 279. Its infrared spectrum contains bands near 3.02 and 4.721, characteristic of the terminal triple bond.

Example 24 E-Prepdration of Sodium amide is prepared from '51 g. (2.2mol) of sodium and 3 liters of liquid ammonia (32"). To this suspensionis added 116 g. (1.1 mol) of and the product is alkylated with 216 g.(1.0 mol) of Br(CH Br. The mixture is stirred for 16 hours while ammoniais permitted to evaporate through a cellophanecapped opening. Theresidue is diluted with water and the organic layer washed with diluteHCl and dried. Distillation results in a recovery of 15 g. of thestarting 1,7-octadiyne and 8.0 g. of 1,7-cyclododecadiyne, M.P. 389.

Analysis.-Calcd. for C H C, 89.9; H, 10.1; M. Wt. 160. Found: C, 89.5;H, 10.2; M.Wt. 152. Its infrared spectrum is free from absorption bands,characteristic of a terminal triple bond. Further distillation producesa yellow oil, B.P. 210-220 at 0.2 mm. Hg which partly solidifies onstanding. Crystallization from a mixture of ether and pentane yields1,7,13,19-cyc1otetracosatetrayne as a white solid, M.P. 7 71Analysis.Calcd. for C l-I C, 90.0; H, 10.0. Found: C, 89.5; H, 9.8. Itsinfrared spectrum is free from absorption bands characteristic of aterminal triple bond.

Example 25 .Preparation of /CEC H2)s ozo Sodium amide is prepared from46 g. (2.0 mol) of sodium and 2 liters of liquid ammonia (-32). To thismixture is added 120 g. (1.0 mol) of and the product is alkyla-ted with173 g. (0.8 mol) of Br(CH Br. The suspension is stirred and the ammoniapermitted to evaporate through a cellophane-capped opening for 16 hours.The residue is diluted with water and the organic layer washed withdilute HCl and dried. Distillation yields 42 g. of1,7-cyclotridecadiyne, B.P. 83-4 at 0.08 mm., M.P. 7, n 1.5060.

Analysis.Calcd. for C H C, 89.7; H, 10.3; M.Wt. 174. Found: C, 89.0; H,10.3; M.Wt. 171. The infrared spectrum is free of bands characteristicof a terminal triple bond.

Further to illustrate the preparation of other compounds of theinvention, the following examples are provided wherein the quantitiesand steps designated (a) and (b) refer to the preparation of a mixtureof mono and disodium acetylide, and step (c) refers to the alkylation,all accomplished via the procedure of the foregoing five examples. 7Example 26.Preparafi0n 0f HCEC(CH )3CEC(CH CEcH (a) NH 3 liters; NaNH 2M from 46 g. (2 M) of Na (b) HCECH, 1.5 moles yielding a 2:1 ratio ofNaC CH to NaC-=CNa (c) Br.(CH Br, 161 g. (0.8 mole) Example 27.-Preparation of H-CEC(CH2)3CEC(CH2)3CEC(CH2)3CEC-H (2.) N11, 3 liters;NaNH- 2 moles from 46 g. (2 M) of Na (e) Br(CH Br, 161 g. (0.8 mole)Example 28.,Preparatian of HCEC(CH CEC(CH ,-CEC(CH CECH (a) NH 3 liters;NaNH 2 moles from 46 g. (2 M) (b I- I CEC(CH CECH, 536g. (4 moles) (c)Br(CH Br, 195 g. (0.8 mole) (a) NH3, f liters;'NaNH 2 moles from 46 g. 2M) (b) H-CEC(CH2)5CEC-H, 60 g. (0.5 mole) (c) Br(CH Br, 122 g. (0.5mole) mole) (c) Br(CH Br, 108 g. (0.5 mole) Example 33.Preparati0n of(CHz)5'"CE 2)5 EC(CH2)5OE (a) NH 4 liters; NaNH 1 mole from 23 g. (1 M)of (b) H-CEC(CH2)5CEC(CH2)5CECH, 107 g. (0.5.

mole) (c) Br(CH Br, 115 g. (0.5 mole) Example 34.Preparati0n 0f(GH2)6OEC(CH2)6 EC-(CHz)a'CE -(a) NH 4 1iters; NaNH 1 mole from 23 g. (lM) of Na (b) HCEC(CH CEC(CH CECH,

mole) (c) Br(CH Br, 122 g. (0.5 mole) Additionally to illustrate thepreparation of mixtures of mono and disodium acetylide, the followingexamples are 1' provided:

Example 35 A suspension of 192 g. (4 moles) of monosodium acetylide (NaCCH) in 2 liters of kerosene (mixture of satu- I rated hydrocarbons) isstirred and heated at 200.until 22.4 liters (STP) of acetylene isevolved. The suspension is cooled to 25 and the agitation stopped topermit the 1 solids to settle. The kerosene is sucked oil and the solidswashed in succession with three 200 ml. portions of petroleum ether, andstored as slurry in petroleum ether.

A Example 36 A 5-1iter three-necked flask is fitted with a reflux condenser, stirrer and gas inlet tube. Ninety-two g. (4 gram atoms) of asodium dispersion (IO-25 microns particle size, containing 0.25% ofaluminum stearate and 0.5% of 1 oleic acid) in 4 liters of xylene isheated to 105 C. Purified acetylene (passed through 90% H and a column.filled with activated alumina) is introduced under the sur-: 1 face ofthe suspension. A total of 78.4 liters (STP, 3.5

To analyze the reaction product a small sample of the produced solids istreated with water and the liberated gas analyzed by means of vaporchromatography. Qnly acetylene is produced, indicating the absence ofunreacted sodium in the solids.

Example 37 Four moles (dry basis) of KOH pellets and 3 moles (activeingredient basis) of commercial calcium carbide are slurried in 1.5liters of butyl carbitol at 150 C. for three hours. Low boiling liquids,mainly water, are permitted to distill out of the reaction flask. Thereaction product is cooled to 50 C. while vigorously stirred. Such asuspension can be used immediately in reactions with dihalides.

Example 38 Four moles (dry basis) of KOH pellets in one liter of diglyme(dimethyl ether of diethylene glycol) are heated with stirring at 170 C.The heterogeneous mass is cooled to 60 C. while continuously andvigorously agitated. The introduction of acetylene produces anexothermic reaction. The flask is externally cooled so that thetemperature is kept at 60 C.:10 C. The addition of acetylene isterminated after 3 moles are absorbed. The temperature is then loweredto 25 C., and such a suspension can be used in alkylation withdihalides.

Example 39 Lithium amide, prepared in liquid ammonia from 21.0 g. (3.0moles) of lithium, is reacted with 2.0 moles of dry acetylene to producea 1:1 molar ratio mixture of monoand dilithium acetylide. Alkylationwith 345 g. (1.5 moles) of pentame-thylene dibromide gives 61 g. (51%yield) of 1,8-nonadiyne and a higher boiling liquid which via vacuumdistillation yields 1,8-cycltetradecadiyne and a filtrate. Heating thefiltrate yields 20.8 g. clear liquid B.P. 11080 C. 0.1 mm. Hg(1,8,15-hexadecatriyne).

Example 40 Potassium amide, prepared from 117.3 g. (3 moles) ofpotassium in liquid ammonia, is reacted with 2.0 moles of acetylene toyield a 1:1 molar ratio mixture of monoand dipotassium acetylides. Thismixture excess) is alkylated with 311 g. (1.35 moles) of1,5-dibr0mopentane. There is thus obtained a mixture of 36.1 g. of 1,8-nonadiyne, 6.6 g. of 1,8,15-hexadecatn'yne and 7.8 g. of a yellow,amine-smelling liquid.

Example 41 Barium amide is prepared in liquid ammonia by adding 49.4 g.(0.36 mole) barium metal to the ammonia; dry acetylene (0.54 mole) ispassed in to provide a 1:1 molar ratio of monoand dibarium acetylides.Alkylation is carried out by adding 69 g. (0.30 mole) of1,5-dibromopentane. There is thus obtained 3.3 g. of 1,8-nonadiyne (n1.4500), 3.3 g. of 1,8,15-hexadecatriyne (11 1.4772) and 0.5 g. of1,8-cyclotetradecadiyne (M.P. 95 100 C.)

It is to be understood that although the invention has been describedwith specific reference to particular embodiments thereof, it is not tobe so limited, since changes and alterations therein may be made whichare within the full intended scope of this invention as defined by theappended claims.

What is claimed is:

1. A cyclic polyyne having the structure:

Re -CEO EGEWRAQ wherein n is a number greater than 0; R and R arealkylene radicals having at least 5 carbon atoms. 2. A cyclic polyynehaving the structure:

CEO

CEO

wherein R and R are alkylene radicals having at least 5 carbon atoms.

3. The method of preparing a cyclic, acetylenic hydrocarbon whichcomprises chemically reacting a dialkali metal acetylide with analkylene dihalide.

4. The method of preparing compounds of the struc- References Cited bythe Examiner UNITED STATES PATENTS 8/1958 Rutledge 260-678 OTHERREFERENCES Donald J. Cram et al.: J. Amer. Chem. Soc., 78, pp.2518-2523, June 5, 1956.

John H. Wotiz et al.: J. Amer. Chem. Soc., 83, pp. 373376, June 20,1961.

DELBERT E. GANTZ, Primary Examiner.

V. OKEEFE, Assistant Examiner.

1. A CYCLIC POLYYNE HAVING THE STRUCTURE: R3<(-C*C-(R4-C*C)-) WHERIN NIS A NUMBER GREATER THAN 0; R3 AND R4 ARE ALKYLENE RADICALS HAVING ATLEAST 5 CARBON ATOMS.